Effect of Flank Rotation on the Photovoltaic Properties of Dithieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene-Based Narrow Band Gap Copolymers.

Side chain engineering has been an effective approach to modulate the solution processability, optoelectronic properties and miscibility of conjugated polymers (CPs) for organic/polymeric photovoltaic cells (PVCs). As compared with the most commonly used method of introducing alkyl chains, the employment of alkyl-substituted aryl flanks would provide two-dimensional (2-D) CPs having solution processability alongside additional merits like deepened highest occupied molecular orbital (HOMO) energy levels, increased absorption coefficient and charger transporting, etc. In this paper, the triple C≡C bond was used as conjugated linker to decrease the steric hindrance between the flanks of 4,5-didecylthien-2-yl (T) and dithieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene (DTBDT) core. In addition, an alternating CP derived from 4,5-didecylthien-2-yl-ethynyl (TE) flanked DTBDT, and 4,9-bis(4-octylthien-2-yl) naphtho[1,2-c:5,6-c']bis[1,2,5]thiadiazole (DTNT), named as PDTBDT-TE-DTNT, was synthesized and characterized. As compared with the controlled PDTBDT-T-DTNT, which was derived from 4,5-didecylthien-2-yl flanked DTBDT and DTNT, the results for exciton dissociation probability, density functional theory (DFT), time-resolved photoluminescence (PL) measurements, etc., revealed that the lower steric hindrance between TE and DTBDT might lead to the easier rotation of the TE flanks, thus contributing to the decrease of the exciton lifetime and dissociation probability, finally suppressing the short-circuit current density (JSC), etc., of the photovoltaic devices from PDTBDT-TE-DTNT.